Olefin oligomerization catalyst and preparation method thereof

Abstract

The invention discloses an olefin oligomerization catalyst and a preparation method thereof. The catalyst is prepared from the following ingredients through being metered by the mass of oxides: 81.0 to 96.0 weight percent of aluminum oxide carriers with macroporous structures (carriers use chitosan as pore-enlarging agents), 2.5 to 11.5 weight percent of active ingredients of ferric sulfate and 1.5 to 7.5 weight percent of nickel sulfate. The olefin oligomerization catalyst has the advantages that the oligomerization activity is high; the dioolymer selectivity is high; the trimer selectivity is low; the operation period of the catalyst is long.

Description

technical field

[0001] The invention belongs to the technical field of olefin oligomerization catalysts, and in particular relates to an olefin oligomerization catalyst and a preparation method thereof, more specifically to an olefin oligomerization catalyst with a macroporous structure of alumina as a carrier and a preparation method thereof. Background technique

[0002] Oligomerization of low-carbon olefins is one of the important chemical processes in oil refining and organic chemical industry. The oligomerization product of butene is an important chemical intermediate, which can be used to produce oligomerized gasoline and diesel oil, as well as detergent, Important intermediates for plasticizers, additives and pesticides. Therefore, butene oligomerization catalysts mainly include heterogeneous catalysts such as Ziggler type homogeneous catalysts, solid phosphoric acid catalysts, zeolite molecular sieve catalysts and supported catalysts. European patent EP0371983 uses ...

Examples

Embodiment 1

[0034] First, 8.0 g of the water-soluble chitosan pore-enlarging agent was added to deionized water at 50° C., and then acetic acid was added dropwise until the chitosan was completely dissolved to obtain an acid solution containing the pore-enlarging agent. Weigh a certain amount of phosphoric acid and potassium nitrate respectively, completely dissolve the phosphoric acid and potassium nitrate in 70 g of distilled water to prepare an aqueous solution containing phosphorus and potassium. Weigh 350g of pseudo-boehmite powder and 20.0g of fennel powder into the kneader, and mix evenly, then add the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, and finally add the acid solution containing chitosan to the pseudo-boehmite The diaspore powder is evenly kneaded, and then kneaded-extruded into a clover shape. Dry at 120° C. for 8 hours, and calcined at 700° C. for 4 hours to obtain an alumina carrier 1 containing phosphorus, lanthanum and potassium. vec...

Embodiment 2

[0037] Add 8.0 g of the water-soluble chitosan pore-enlarging agent into deionized water at 50° C., and then add acetic acid dropwise until the chitosan is completely dissolved to obtain an acid solution containing the pore-enlarging agent. Weigh a certain amount of phosphoric acid and potassium nitrate respectively, completely dissolve phosphoric acid, lanthanum nitrate and potassium nitrate in 70 g of distilled water to prepare an aqueous solution containing phosphorus and potassium. Weigh 350g of pseudo-boehmite powder and 20.0g of fennel powder into the kneader, and mix evenly, then add the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, and finally add the acid solution containing chitosan to the pseudo-boehmite The boehmite powder is evenly kneaded, and then kneaded-extruded into a clover shape. Dry at 120° C. for 8 hours, and calcined at 700° C. for 4 hours to obtain an alumina carrier 2 containing phosphorus, lanthanum and potassium. carrie...

Embodiment 3

[0041] The preparation method of the carrier was carried out according to Example 1. The difference is that the water-soluble chitosan pore-enlarging agent is replaced by the non-water-soluble chitosan pore-enlarging agent, and the chitosan formic acid solution is stirred with a magnetic stirrer for 30 minutes to obtain the alumina carrier 3 with a macroporous structure. The content of the auxiliary components phosphorus, lanthanum and potassium in the carrier accounts for the percentage of the carrier mass, which is P 2 o 5 1.2wt%, La 2 o 3 1.5%, K 2 O 1.4 wt%. Its specific surface area and pore size distribution are shown in Table 1.

[0042] Ferric sulfate hexahydrate and nickel sulfate hexahydrate were prepared as an impregnating solution, and 100 g of alumina carrier with a macroporous structure was impregnated. The specific steps were the same as in Example 1. The catalyst was dried at 130°C for 7h and then calcined at 550°C for 7.0h to obtain isobutylene oligome...

technical field

[0001] The invention belongs to the technical field of olefin oligomerization catalysts, and in particular relates to an olefin oligomerization catalyst and a preparation method thereof, more specifically to an olefin oligomerization catalyst with a macroporous structure of alumina as a carrier and a preparation method thereof. Background technique

[0002] Oligomerization of low-carbon olefins is one of the important chemical processes in oil refining and organic chemical industry. The oligomerization product of butene is an important chemical intermediate, which can be used to produce oligomerized gasoline and diesel oil, as well as detergent, Important intermediates for plasticizers, additives and pesticides. Therefore, butene oligomerization catalysts mainly include heterogeneous catalysts such as Ziggler type homogeneous catalysts, solid phosphoric acid catalysts, zeolite molecular sieve catalysts and supported catalysts. European patent EP0371983 uses ...

Examples

Embodiment 1

[0034] First, 8.0 g of the water-soluble chitosan pore-enlarging agent was added to deionized water at 50° C., and then acetic acid was added dropwise until the chitosan was completely dissolved to obtain an acid solution containing the pore-enlarging agent. Weigh a certain amount of phosphoric acid and potassium nitrate respectively, completely dissolve the phosphoric acid and potassium nitrate in 70 g of distilled water to prepare an aqueous solution containing phosphorus and potassium. Weigh 350g of pseudo-boehmite powder and 20.0g of fennel powder into the kneader, and mix evenly, then add the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, and finally add the acid solution containing chitosan to the pseudo-boehmite The diaspore powder is evenly kneaded, and then kneaded-extruded into a clover shape. Dry at 120° C. for 8 hours, and calcined at 700° C. for 4 hours to obtain an alumina carrier 1 containing phosphorus, lanthanum and potassium. vec...

Embodiment 2

[0037] Add 8.0 g of the water-soluble chitosan pore-enlarging agent into deionized water at 50° C., and then add acetic acid dropwise until the chitosan is completely dissolved to obtain an acid solution containing the pore-enlarging agent. Weigh a certain amount of phosphoric acid and potassium nitrate respectively, completely dissolve phosphoric acid, lanthanum nitrate and potassium nitrate in 70 g of distilled water to prepare an aqueous solution containing phosphorus and potassium. Weigh 350g of pseudo-boehmite powder and 20.0g of fennel powder into the kneader, and mix evenly, then add the mixed solution of phosphoric acid, lanthanum nitrate and potassium nitrate, and finally add the acid solution containing chitosan to the pseudo-boehmite The boehmite powder is evenly kneaded, and then kneaded-extruded into a clover shape. Dry at 120° C. for 8 hours, and calcined at 700° C. for 4 hours to obtain an alumina carrier 2 containing phosphorus, lanthanum and potassium. carrie...

Embodiment 3

[0041] The preparation method of the carrier was carried out according to Example 1. The difference is that the water-soluble chitosan pore-enlarging agent is replaced by the non-water-soluble chitosan pore-enlarging agent, and the chitosan formic acid solution is stirred with a magnetic stirrer for 30 minutes to obtain the alumina carrier 3 with a macroporous structure. The content of the auxiliary components phosphorus, lanthanum and potassium in the carrier accounts for the percentage of the carrier mass, which is P 2 o 5 1.2wt%, La 2 o 3 1.5%, K 2 O 1.4 wt%. Its specific surface area and pore size distribution are shown in Table 1.

[0042] Ferric sulfate hexahydrate and nickel sulfate hexahydrate were prepared as an impregnating solution, and 100 g of alumina carrier with a macroporous structure was impregnated. The specific steps were the same as in Example 1. The catalyst was dried at 130°C for 7h and then calcined at 550°C for 7.0h to obtain isobutylene oligome...

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